Extraction of metals with diquaternary amines

ABSTRACT

Selective extraction of one or more metal anions from an aqueous solution, by contacting the aqueous solution with an organic solution including a diquaternary amine, wherein the diquaternary amine has two diquaternary nitrogens spaced at a distance of less than about 10 Å, selectively binding the metal anions to the diquaternary amine, and then separating the organic solution from the aqueous solution, wherein the diquaternary amines having the selectively bound metal anions are concentrated in the organic solution. Alternatively, the diquaternary amines may be adsorbed or chemically bonded to a solid, and the metal anion-containing aqueous solution passed over the solid having the diquaternary amines. Palladium may be selectively extracted by contacting the acidic solution with an iodide and an organic solvent, allowing the palladium to bind to the iodide, and then separating the organic solution from the aqueous solution, concentrating the bound palladium ions in the organic solution.

[0001] This application is a continuation of U.S. application Ser. No.10/071,872 filed on Feb. 7, 2002.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates to an extractant and an extractionprocess. More particularly, the invention relates to an extractantuseful for extracting metal ions from an aqueous solution.

[0004] 2. Description of the Related Art

[0005] The platinum group metals (PGMs) are exceedingly rare in naturewith average crustal quantities of only a few fractions of apart-per-million (ppm). Only a few large deposits of platinum groupmetals are known to exist and these deposits are located in South Africaand Russia. Smaller quantities of PGMs are obtained from the anodeslimes produced during the electrorefining of nickel and from a fewsmall mineral deposits variously located around the world. The growingdemand for platinum group metals and other precious metals inhigh-technology applications has generated a demand for methods andprocesses for recycling these materials, especially from spent catalystsand from electronic scrap. It is important that PGMs be recycled becauseof the limited natural supply of these elements.

[0006] PGMs are used as catalysts in the chemical and automotiveindustry and as oxidation resistant coatings in the electronics sector.Many of these uses, especially the catalytic uses, are ideal forrecovering the PGMs because the spent catalyst may be easily processedfor metal recovery as part of the disposal process for the spentcatalysts. Therefore, there is an interest in improving the methods andprocesses used for recovering PGMs by making these methods and processesfaster and more efficient.

[0007] Using traditional smelting techniques to treat materials such asspent catalysts or electronic scrap is not always effective due to therefractory nature and low precious metal content of the spent catalystsand electronic scrap. Leaching spent catalysts and other scrap materialswith acidic chloride solutions containing an oxidizing agent iseffective in removing the precious metals and has the added advantage ofpreserving valuable substrates for recycling. However, the recovery andsubsequent separation of precious metals, including PGMs, from thechloride feed liquors constitutes a difficult problem because theseliquors often contain only low levels of precious metals (ppm levels)but high levels (on the order of grams per liter) of base metals such asiron, copper, zinc, tin, and nickel. Moreover, the volumes of solutionsgenerated from the acid recovery of precious metals from spent catalystsand the like are large compared to the volume of highly concentratedsolutions generated from typical precious metal refining. Classicalprecipitation techniques are inefficient when applied to such solutionsand these classical techniques are being replaced by modern separationmethods such as solvent extraction processes.

[0008] Solvent extraction, sometimes referred to as liquid ion exchangeextraction, takes place in two steps. In the first step, the extractionstep, a dilute aqueous feed solution containing the metal ion to berecovered is mixed with an immiscible hydrocarbon carrier containing anextractant dissolved therein. When the metal ion contacts theextractant, a metal complex is formed that migrates to the organicphase. In the second step, the stripping step, the “loaded” organicphase, which has been separated from the aqueous feed solution, is mixedwith another aqueous solution of a stripping agent (e.g., sulfuric acid)wherein the metal ion passes to the aqueous stripping phase. Therefore,the extraction process converts a dilute feed solution of metal ionsinto a highly concentrated solution of the precious metal ions fromwhich the metals may be more readily recovered, e.g., by electrolysis.The barren organic phase may then be recycled through the system ifdesired.

[0009] Monoquaternary amines have been somewhat effective in recoveringplatinum group metals from acidic process streams containing base metalssuch as nickel and cobalt. Monoquaternary amines contain a positivelycharged nitrogen atom having four groups bonded to the nitrogen atom,and another atom or substituent that neutralizes the positive charge,typically a hydroxide or a chloride. However, the monoquaternary aminescurrently used in separation processes are not highly selective,although some selectivity has been achieved by modifying the substituentgroups on the quaternized nitrogen atom or by carefully selecting theorganic solvent used as a diluent. A monoquaternary amine currentlybeing used in extracting PGMs is N-methyl-N,N-dioctyl-1-octanaminiumchloride. (Available as ALIQUAT 336, a registered trademark of theHenkel Corporation of Germany).

[0010] In extracting PGMs from an aqueous acidic solution using amonoquaternary amine, the monoquaternary amine is first dissolved in apredominately water-immiscible or organic phase, such as 1-octanol. Theaqueous and the organic solutions are then intimately mixed to allow thedissolved quaternary amine salt to form an ion pair with the PGM andtransfer the desired PGM species from the aqueous phase into the organicphase. The two phases can then be separated and the extracted anionrecovered from the organic phase.

[0011] A monoquaternary amine has also been adsorbed onto an inertpolymeric support, while still retaining its desirable anion exchangeproperties, by making a slurry of the quaternary amine in methanol withresin beads and slowly removing the methanol using a rotary evaporator,leaving the monoquaternary amine adsorbed onto the surface of the resinbeads. Since the monoquaternary amine is not covalently attached, butonly held by weak Van der Waals attractions, the selectivity inextracting PGMs is similar to that of the free monoquaternary amine. Inextraction systems, it is preferable for the extractant to beimmobilized on a solid support because it eliminates the organicsolvent, thereby making processing simpler with fewer environmentalconcerns.

[0012] What is needed is a more selective extractant compound forextracting precious metals, such as PGMs, from acidic solutions. Itwould be an advantage to provide a method for designing an efficientextraction compound having a high selectivity for a particular preciousmetal.

SUMMARY OF THE INVENTION

[0013] The present invention provides a method for selectivelyextracting one or more metal anions from an aqueous solution, the methodcomprising contacting the aqueous solution with an organic solutionincluding a diquaternary amine, wherein the diquaternary amine has twodiquaternary nitrogens spaced at a distance of less than about 10 Å,selectively binding the metal anions to the diquaternary amine; and thenseparating the organic solution from the aqueous solution, wherein thediquaternary amines having the selectively bound metal anions areconcentrated in the organic solution.

[0014] The method may be used to extract one or more platinum groupmetals, preferably platinum, palladium, rhodium, and combinationsthereof. The diquaternary amines are selective and may selectivelyextract desired metals from an aqueous solution containing the desiredmetal anions as well as contaminant metals. The contaminant metals maybe, for example, selected from Pb, Al, Ba, Ce, Zr, Fe, Cu, Co, Ni, Mo,Sn, Sb, As, Bi, Zn, Na, K, Ca and combinations thereof. Examples ofvaluable metals that the diquaternary amines may selectively extract areselected from Ag, Au, Pd, Rh, Pt, Ru, Os, Ir, and combinations thereof.Preferably, the diquaternary amines are used to selectively extract oneor more metal anion complex, wherein the distance between the twodiquaternary nitrogens allows both diquaternary nitrogens tosimultaneously interact with the one or more metal anion complex. Inother words, the one or more metal anion complex that has been targetedto be selectively extracted should have a size compatible with forming acomplex between both diquaternary nitrogens. It is believed that thissimultaneous interaction or complexing occurs when the distance betweenthe two diquaternary nitrogens is within about 5 Angstroms of the sizeof the complex, either greater or smaller.

[0015] The method is not limited to any particular pH of the aqueoussolution, but metals are typically dissolved in acidic solutions. Theseacidic aqueous solutions may contain an acid selected from hydrochloricacid, sulfuric acid, nitric acid, any other acid that may dissolve themetals to be extracted, and combinations thereof. The acid concentrationmay be of any concentration that dissolves the metal anions to beextracted. The diquaternary amines effectively extract valuable metalsat any acid concentration. However, it should be emphasized that animportant advantage of the present invention is that any solution thatcontains dissolved metals to be extracted is suitable for the method ofthe present invention, whether the solution is a base solution, aneutral solution or an acidic solution.

[0016] The aqueous solution is contacted with the organic solution for atime period suitable of less than about 30 minutes, preferably less thanabout 20 minutes, and more preferably between about 5 minutes and about20 minutes.

[0017] The concentration of the diquaternary amines within the organicsolution is any concentration up to saturation, preferably between about0.5 wt % and about 10 wt %, more preferably between about 0.5 wt % andabout 6 wt %, and most preferably between about 1 wt % and about 5 wt %.Preferably there is a molar excess of diquatemary amines in the organicsolution over the amount of metal anion to be extracted. The organicsolution has an organic solvent able to dissolve the selected one ormore diquats and is immiscible with water, preferably selected fromchloroform, 1-octanol, methanol, and combinations thereof.

[0018] The diquaternary amines are diquaternary ammonium halides thatare substantially insoluble in water. The diquaternary amines mustprovide a distance between the two diquaternary nitrogens that allowsthe formation of a complex between both diquaternary nitrogens and theone or more metal anion complex to be selectively extracted. Thiscomplex between the diquaternary nitrogens and one or more metal anioncomplex may be formed when the two diquaternary nitrogens are separatedby a structure including, without limitation, an alkyl chain that may beeither saturated or unsaturated and either straight or branched, or aheterocyclic ring structure that may be either saturated or unsaturatedand either substituted or unsubstituted. In the simplest embodiments,the structure that links the two diquaternary nitrogens will having fromabout 2 to about 8 carbon atoms separating the two diquaternarynitrogens, although additional carbon atoms may be present in sideschains or portions of the ring structure that do not affect the spacingof the nitrogens. It is the spacing of the two diquaternary nitrogensthat is most important, and the foregoing structures between the twodiquaternary nitrogens should be construed to include all possiblehydrocarbon structures. While the halogen may be fluorine, chlorine,bromine or iodine, the halogen is preferably selected from iodine andchlorine.

[0019] The method of the present invention is not limited to dissolvingthe diquaternary amine in an organic solvent. Alternatively, thediquaternary amines may be immobilized on a solid surface, such as aresin or a polymer. In this embodiment, the aqueous solution is mixed orflows over the solid phase having the attached diquaternary amines,wherein the diquaternary amines extract the metal anions from theaqueous solution. The diquaternary amines may be bonded to the solidsurface by adsorption or by chemical bonding.

[0020] The present invention further provides a method for selectivelyextracting palladium from an aqueous solution. The method comprisescontacting the aqueous solution with an iodide and an organic solvent,allowing the palladium to bind to the iodide, and then separating theorganic solution from the aqueous solution, wherein the KI having thebound palladium ions are concentrated in the organic solution.

[0021] The present invention further provides a method for firstselectively extracting palladium from a mixture of metal anions with aniodide and then selectively extracting other metal anions with thediquaternary amines. The method comprises dissolving the metals into anacidic solution, contacting the acidic solution with an iodide,separating the iodide from the acidic solution, wherein the Pd is boundto the iodide, contacting the acidic solution with an organic solutionincluding a diquaternary amine, wherein the distance between twodiquaternary nitrogens is less than about 10 Å, selectively binding thePt anions to the diquaternary amine, and then separating the organicsolution from the aqueous solution, wherein the diquaternary amineshaving the selectively bound Pt anions are concentrated in the organicsolution. The iodide may be either an organic iodide, such as adiquaternary amine iodide, or an inorganic iodide, such as potassiumiodide.

[0022] The foregoing and other objects, features and advantages of theinvention will be apparent from the following more particulardescription of a preferred embodiment of the invention, as illustratedin the accompanying drawing wherein like reference numbers representlike parts of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

[0023]FIG. 1 shows the structures of the diquaternary amines that weresynthesized.

[0024]FIG. 2 is a graph showing the percent metal extracted from anaqueous solution containing Rh, Pd, Ni, Fe, Co, and Cu for selectedextractants.

[0025] FIGS. 3A-3C is a table showing the calculated values fordifferent properties of the synthesized diquaternary amines.

[0026] FIGS. 4A-4E are graphs of equations that may be used to predictselectivity of structurally related diquaternary amines for Pd II, PdIV, Pt II, Pt IV and Rh III.

[0027]FIG. 5 is a chart showing the metal concentrations at differentstages of a metal recovery experiment using an embodiment of the metalrecovery method of the present invention.

DETAILED DESCRIPTION

[0028] The present invention provides a method for using diquaternaryamine compounds or extractants to extract anions of platinum groupmetals and other metals from an aqueous solution. The diquaternary aminecompounds have tailor-made properties that enhance their ability toextract platinum group metals and other metals from aqueous solutions.Platinum group metals (PGM) include platinum, palladium, rhodium,iridium, ruthenium and osmium. The interaction between the diquaternaryamines of the present invention and the metal anions is specific basedupon a favorable spatial arrangement so that the metal anions may betrapped selectively, providing a strong interaction that traps the metalanion as a stable pair.

[0029] The strong interaction and the favorable spatial arrangementprovided by the diquaternary amines of the present invention areachieved by linking two quaternary amines together with a shortaliphatic carbon chain or a small ring, thereby forming a diquaternaryamine compound that provides a strong interaction and the favorablespatial arrangement with the target metal anion. Optionally, it shouldbe noted that the chain or the ring may be saturated or unsaturated. Bychanging the length or size of the chain or ring between the amines,different diquaternary amine compounds may be synthesized having desiredspatial arrangements, because the longer the chain or the larger thering, the farther apart will be the two nitrogens in the resultingdiquaternary amine. Therefore, to extract a larger anion, a diquaternaryamine may be designed having a longer chain or a larger ring. To extractan anion having a smaller size, a diquaternary amine may be designedhaving a shorter chain or a reduced ring size. Because the diquaternaryamine “grips” the metal complex anion between the two nitrogen atoms, ifthe anion is significantly smaller than the space between the nitrogens,then the anion will not be selectively extracted because the anion isnot large enough to be attracted by both nitrogen atoms at the sametime, but only by the lesser attraction of whichever one is closer.Conversely, if the metal anion complex size is much larger than thespace between the nitrogens, then the metal anion complex may be lessselectively extracted since the anion will not be attracted stronglybetween the nitrogen atoms. However, because the larger-size anion maystill interact with both nitrogen atoms, some selectivity seems to beretained so long as the size of the metal anion complex can stillinteract with both of the nitrogens of the diquaternary amine. Thespatial characteristics of the distance between the two positivelycharged nitrogen ions thereby leads to a degree of shape and/or sizeselectivity for specific anions.

[0030] The distance between the two quaternary nitrogens does notdecrease linearly with the decrease in the number of methylene groupsseparating them. The distance between two quaternary nitrogens separatedby five methylene groups was found to be 7.55 Å decreasing to 3.57 Åwith only two methylene groups. The distance was found to be 3.03 Å witha cyclical piperazine derivative. The distance between the nitrogensalso changed as a function of the substituent around the nitrogen. Incomparison, the average ionic size of the platinum metal halidecompounds has been predicted to be about 3 Å.

[0031] The diquaternary amines used as extractants in the presentinvention were synthesized by combining tertiary diamines with astoichiometric molar excess of alkyl halides to produce diquaternaryammonium halides. The preferred alkyl halides are the alkyl chlorides,such as 1-Chloro octadecane or 1-Chlorodecane, or the alkyl iodides,such as 1-Iodo octadecane or 1-Iododecane. The alkyl halides should beselected to ensure that the diquaternary amines have low watersolubility, such as an alkyl halide having ten carbon atoms. If thestarting tertiary diamines already have low water solubility, or if theextraction process does not require the diquaternary amine to bedissolved in an organic phase to facilitate separation from the aqueousphase during the extraction process, then other alkyl halides with fewercarbon atoms would be suitable. However, in the examples disclosedherein, water insolubility of the diquaternary amine is ensured byincluding an alkyl halide with an alkyl group having at least ten carbonatoms.

[0032] Exemplary diquaternary ammonium halides may be prepared by thefollowing synthesizing schemes:

[0033] wherein R₁-R₆ are each independently selected from hydrogen andorganic groups, and wherein n is an integer from 2 to about 8. Aromaticdiquaternary amines would be similarly synthesized. In accordance withthe invention, the chain between the two diquaternary ammoniums may beeither saturated or unsaturated and either straight or branched, or thering between the two diquaternary ammoniums my be either saturated orunsaturated and either substituted or unsubstituted.

[0034] The prepared diquaternary amine salts were precipitated as whitecrystalline solids. Some of the solid diquaternary amines were stored incapped vials in a lab room at room temperature for up to six months. Nodegradation or decomposition was observed during these six months norwas the extracting ability of the stored diquaternary amines affectedwhen compared with freshly prepared compounds. The diquaternary aminesof the present invention therefore appear to be very stable compoundsthat can be stored for long periods of time without degrading.

[0035] The diquaternary amines thus synthesized are useful forextracting platinum group metals and other precious/valuable metals fromaqueous solutions, preferably acidic solutions, wherein the metals forman anion complex. The method is not limited only to extracting metalsfrom acidic solutions, but from extracting metal anions from any aqueoussolution having any pH. The extraction method comprises contacting theaqueous solution with the diquaternary amines so that the metals maycome into contact with the diquaternary amines, wherein a complex isformed between the diquaternary amine and the metal. In effect, thecomplex allows the diquaternary amine to “capture” or extract the metalfrom the aqueous solution. After the aqueous solution has contacted thediquaternary amine for a sufficient time, a separation step is requiredwherein the aqueous solution is separated from the diquaternary amine,leaving the metals with the diquaternary amine. If the diquaternaryamine is dissolved in an organic solvent that is not miscible withwater, then the separation is achieved by separating the aqueoussolution from the immiscible organic solution.

[0036] Alternatively, the diquaternary amine may be immobilized on aresin or other surface of an inert substrate or polymer, wherein theseparation step involves separating the aqueous solution from a solidphase having a surface on which the diquaternary amines are eitheradsorbed or chemically bonded. The diquaternary amines may be adsorbedonto the surface as described above for a monoquaternary amine orchemically bonded to a resin bead or similar inert substrate or polymerby including a specially functionalized substituent in the diquaternaryamine that can chemically bond to a polymer backbone duringpolymerization or be chemically attached later on to the inertsubstrate. For example, in synthesizing the diquaternary amine, thesubstituent added to the tertiary amines to synthesize the diquaternaryamine may include an additional active substituent, such that after thediquaternary amine is synthesized, the active substituent may be broughtinto contact with a polymer and then bind itself to the polymer underfavorable reaction conditions.

[0037] When the diquaternary amine is dissolved in an organic solvent tofacilitate the separation step of the extraction method, any organicsolvent that is immiscible with water would be suitable. A preferredorganic solvent is 1-octanol for most of the diquaternary amines.However, to improve the solubility for some of the diquaternary aminesin 1-octanol, the addition of chloroform and/or methanol is helpful. Amore preferred organic solvent is chloroform because using chloroform asthe solvent improves the extraction of the precious metals from theaqueous solution. Table 1 presents a table showing the effect of solventselection on the extraction of rhodium and platinum using selecteddiquaternary amines. Organic solutions of the diquaternary amines mayhave concentrations up to saturation, preferably up to about 10 wt %diquaternary amines. More preferably, the concentrations will range from0.5 wt % to about 5 wt %. Most preferably, the concentrations will rangefrom about 1 wt % to about 5 wt %. TABLE 1 DQ ID Chloroform OctanolPercent Rh III Removed from a 3 M HCl Solution  9I 88.35 63.92 11I 87.4863.40 17I 87.00 59.73 Percent Pt III Removed from a 3 M HCl Solvent 10Cl98.46 89.50 11Cl 96.77 53.56 12Cl 91.42 77.14 13Cl 98.14 99.86 14Cl99.45 97.61

[0038] The required contact time between the diquaternary amine and theaqueous solution during the extraction process is determined by thekinetics of the extraction process. It is desirable to carry out anextraction process in as short a time period as possible to minimize theoperating costs. In the method of the present invention, contact timemay be less than 30 minutes, preferably less than 20 minutes, and mostpreferably between about 5 minutes and about 20 minutes.

[0039] The metals that may be extracted using this method includeplatinum group metals and other precious metals. The metals include, forexample, platinum, palladium, rhodium, iridium, osmium, ruthenium, gold,silver and combinations thereof. However, the method of the presentinvention is not limited only to these metal anion complexes but may beused to extract any desired metal anion complex that is attracted to thediquaternary nitrogen atoms and that has an anion complex size similarto the distance between the two diquaternary nitrogen atoms.

[0040] Recovering precious metals from spent catalysts, electronic scrapand other similar sources include mixing these precious metal-containingmaterials with a strong acid, such as sulfuric acid, nitric acid and/orhydrochloric acid to dissolve the metals into an aqueous acidic solutionfrom which the metals may be extracted through an extraction process.While traditionally these metals are dissolved in acidic solutions, thepresent method is not limited to recovering metal anion complexes onlyfrom acidic solutions, but from an aqueous solution having any pH. Theresulting acidic solutions containing the precious metals to beextracted will also contain contaminant metals and other materialsdissolved by the acid from the spent catalyst and electronic scrap.These contaminant metals often have a higher concentration level in theacidic solution than the desired precious metals, and may include Pb,Al, Ba, Ce, Zr, Fe, Cu, Co, Ni, Mo, Sn, Sb, As, Bi, Zn, Na, K, Ca andcombinations thereof.

[0041] Selected diquaternary amines have shown good selectivity betweenthe contaminant metals and the precious metals when tested in aqueoussolutions containing Rh, Pd, Ni, Fe, Co, and Cu. FIG. 2 is a graphshowing the percent metal extracted from an aqueous solution containingRh, Pd, Ni, Fe, Co, and Cu for different selected diquaternary amines ofthe present invention, as well as the commercially availablemonoquaternary amine ALIQUAT 336. The metals were extracted from a 3 Mhydrochloric acid (HCl) solution containing 50 ppm of each of the metalcomponents using organic solutions having the selected diquaternaryamines in concentrations of 2.5 wt %.

[0042] The acidity of the aqueous solution may affect the efficacy ofthe extraction process when using the diquaternary amines. In the caseof platinum and rhodium, it has been found that a wide range of acidityis acceptable for the diquaternary amines to extract the metal, withsome diquaternary amines performing better than others for a givenacidity. A lower acidity is preferred for extracting palladium. Tables 2through 4 show the effect that the acidity of the aqueous solution hason the ability of selected diquaternary amines to extract platinum,palladium and rhodium. Table 2 shows the effect of differing acidconcentrations on the performance of selected diquaternary amines inextracting Pd II and Pd IV from a 50 ppm solution of the metal. Table 3shows the effect of differing acid concentrations on the performance ofselected diquaternary amines in extracting Pt II and Pt IV from a 50 ppmsolution of the metal. Table 4 shows the effect of differing acidconcentrations on the performance of selected diquaternary amines inextracting Rh III from a 50 ppm solution of the metal. TABLE 2 0.5 M HCl3 M HCl 10 M HCl 0.5 M HCl 3 M HCl 10 M HCl Diquat ID Pd II Pd II Pd IIPd IV Pd IV Pd IV 10 Cl NA 63.62 25.66 99.46 86.48 28.29 13 Cl 63.2276.31 39.16 98.00 91.69 35.55 14 Cl 98.54 72.25 55.27 99.11 74.75 51.2018 Cl 99.68 74.06 53.87 99.76 91.39 49.21 Aliquat 336 85.22 27.25 49.9377.87 28.52 34.27

[0043] TABLE 3 0.5 M HCl 3 M HCl 10 M HCl 0.5 MH Cl 3 M HCl 10 M HClDiquat ID Pt II Pt II Pt II Pt IV Pt IV Pt IV 10 Cl 99.82 89.50 99.8298.91 97.45 98.91 13 Cl 99.80 99.86 99.80 100.00 100.00 100.00 14 Cl100.00 97.61 100.00 100.00 100.00 100.00 18 Cl 100.00 100.00 100.00100.00 97.65 100.00 Aliquat 336 96.82 46.25 96.82 86.21 63.54 86.21

[0044] TABLE 4 0.5 M HCl 3 M HCl 10 M HCl Diquat ID Rh III Rh III Rh III11 Cl 2.85 12.99 12.28 13 Cl 24.54 35.61 20.04 14 Cl 14.70 22.05 30.8418 Cl 0.0 9.64 11.50 Aliquat 336 2.77 0.00 0.00

[0045] Not all diquaternary amines are equally effective in extracting agiven precious metal from an aqueous solution. Table 5 illustrates themetal anion selectivity demonstrated by selected diquaternary chlorideamines in extracting metal anion complexes from an aqueous solutioncontaining equal concentrations of the extracted metals. As shown inTable 5, the diquaternary amines were most effective in extracting Pt,with Pd being the next most successful metal to be extracted. Rhodiumwas the least successful to be extracted. However, it should be notedthat the diquaternary amines having a distance of 3.03 Å, 3.10 Å, 5.21Å, and 5.36 Å between the two nitrogens performed best in extracting themetal halide compounds, having an estimated size of about 3 Å. Thissupports the present conclusion that the performance of the diquaternaryamines in extracting metals from an aqueous solution depends on thedistance between the nitrogens. Therefore, diquaternary amines may bedesigned to extract metals from a solution based upon the size of themetal to be extracted. TABLE 5 N Spacing Rh % Pt % Pd % Diquat ID ÅExtracted Extracted Extracted 10 Cl 8.3 0 86 76.62 11 Cl 3.68 0 61.6441.26 12 Cl 8.6 0 53.31 53.02 13 Cl 3.03 21.94 100 95.67 14 Cl 3.10 1.95100 88.00 15 Cl 0.66 0 38.49 26.49 17 Cl 5.21 1.12 92.83 56.46 18 Cl5.36 0 98.63 80.71 Aliquat 336 0 39.01 30.05

[0046] As may be seen from Table 6, the diquaternary iodides are muchbetter extractants for rhodium than the diquaternary chlorides. TABLE 6Diquat ID 9 I 10 I 11 I 12 I 13 I 14 I 15 I 16 I 17 I 18 I Aliquat 336Rh III % Extracted 88 47 87 50 86 71 64 69.7 87 57 30

[0047] The inventors have also discovered that iodide ions form acomplex with the Pd ions in the aqueous acidic solution, rendering thePd-iodide complex highly soluble in organic solvents. Therefore, Pd maybe removed from an acidic aqueous solution simply with the addition ofan iodide ion, such as provided by KI dissolved in a solvent such asoctanol or chloroform. By adding the iodide, the palladium ions migrateto the organic phase from the aqueous phase, thereby providing animportant tool for the separation of Pd from other precious andcontaminant metals. The KI may be added to the aqueous solution or tothe organic solvent used to recover the palladium, but preferably to theaqueous solution. Other inorganic or organic iodides are acceptable suchas NaI, CaI, MgI, monoquaternary amine iododies, alkyl iodides and otherorgano iodides. The iodide concentration in the solvent is not criticalbut there should be a molar excess to the metal complex anion. Theorganic solvent may be any organic solvent that dissolves the metaliodide and is immiscible in water. Contact time should be between lessthan about 45 minutes, preferably between about 5 minutes and about 30minutes.

[0048] A two step process for selectively extracting precious metalsfrom spent catalyst taken from automobile catalytic converters isbeneficial. Platinum and palladium are both used in catalytic convertersand may be selectively extracted from an acidic solution containingthese metals by using a two step process of the present invention.First, the palladium is removed by contacting the acidic solution withan iodide as described above. After separating the organic solutioncontaining the palladium, the acidic solution is contacted with a secondorganic solution containing a diquaternary amine that selectivelyextracts the platinum.

[0049] Extracting palladium first by using iodide is beneficial becauseit allows the diquaternary amines to be used for extracting only theplatinum. This provides a separation technique not only for extractingthe precious metals from the contaminant metals, but also for obtainingthe palladium separate from the platinum.

[0050] Quantitative Structure Activity Relationship (QSAR) analysis wasused on the synthesized diquaternary amines to determine whether therewas a predictive relationship for determining whether a particulardiquaternary amine, having a given carbon chain length, would besuccessful as an extractant for specific precious metal ions. Theexperimental data obtained for the 10 synthesized diquaternary amineswas used to determine a quantitative relationship between the bindingabilities of various diquaternary amines and their structuralproperties. The quantitative relationships derived herein from thelimited experimental data available is not meant to be definitive, butdemonstrates a method that may be used to design a particulardiquaternary amine suitable for selectively extracting a given metalanion complex or group of metal anion complexes.

[0051] This quantitative relationship may be used to predict whether agiven diquaternary amine would be a good extractant for a particularmetal anion. To determine the quantitative relationship, variouschemical, physical, topological and electronic descriptors are firstcalculated using empirical equations based upon the structure of thecompound. Fifteen different properties were calculated with the resultsshown in FIGS. 3A-3C.

[0052] Next, the experimental values from the solvent extractionexperiments were converted into distribution ratios, or D Values. The DValues represent the ratio of the amount of metal ion concentrationextracted in the organic phase versus the amount of metal ionconcentration remaining in the aqueous phase, as defined by:

D=[PGM] _(org) /[PGM] _(aq)

[0053] Next, these D Values were plotted as experimental D Values ongraphs as shown in FIGS. 4A through 4E. Correlations between thecalculated properties shown in FIG. 3 and the D Values were determinedand analyzed by viewing scatter plots. The properties that gave the bestfits were used to generate multiple regression analysis columns. Theresulting equations may be used to predict selectivity of structurallyrelated diquaternary amines for future research and applications. FIGS.4A through 4E further show the prediction equations for Pd II, Pd IV, PtII, Pt IV and Rh III.

EXAMPLE 1

[0054] Ten diquaternary iodide amines and eight diquaternary chlorideamines were synthesized in accordance with the present invention. Eachof the synthesized diamines was synthesized from one of the followingfive different diamines: N,N,N,N-Tetramethylethylenediamine (TMED),N,N,N′,N′-Tetramethyl-1,4-butanediamine (TMBD),N,N,N′,N′-Tetramethyl-1,3-propanediamine (TMPD),N,N,N′,N′-Tetramethyl-1,6-hexanediamine (TMHD), or1-4-Dimethylpiperazine (DMP). To synthesize one of the diquaternaryamines, 10 mM (millimoles) of a diamine selected from those listedabove, was added to 25 ml of dimethyl formamide in a 200 ml round bottomflask. An alkyl halide was added to this solution at a molar excess ofeither 4 times or 6 times the stoichiometric requirement. For astoichiometric molar excess of 4 times, 40 mM of 1-chloro octadecane(COD) or 1-iodo octadecane (IOD) was added. For a stoichiometric molarexcess of 6 times, 60 mM of 1-chlorodecane (CD) or 1-iododecane (ID) wasadded. Then 0.2 g of sodium carbonate was added along with a stir bar.

[0055] The flask was then placed in a heated oil bath and magneticallystirred. The oil bath was maintained at 75° C. for the synthesis ofiodide diquats and 115° C. for the synthesis of chloride diquats. Theflask was capped with a 20° C. water-cooled reflux condenser, sealedwith a rubber septum and vented with a syringe needle. The reactionmixture was then sparged with argon, heated, and stirred for 48 hours.

[0056] Synthesized iodide diquaternary amines were precipitated by thedrop wise addition of the reaction mixtures in 100 ml of benzene whilethe synthesized chlorides were precipitated in a 50 ml:50 ml mixture ofhexanes-benzene. The solutions were then kept cooled to −15° C.overnight. Precipitates were isolated by vacuum filtration on mediumfine filter paper, washed with an additional 20 ml of respective solventand then vacuum dried overnight. Products were weighed, sealed in glassvials, labeled and stored at 5° C. until further use. Yields of thediquats were nearly quantitative and the overall yields of iodidediquats were higher than those of the chlorides. Two of the chloridediquats, referred to in FIG. 1 as 9Cl and 16Cl, were unable to beprecipitated out using these procedures. The diquaternary aminessynthesized by this method are shown in FIG. 1. The identificationnumbers used to refer to the diquaternary amines in FIG. 1 was adoptedfor convenience and has no relevance to the actual structure of thediquats, except that “Cl” refers to the chloride form of the diquat(abbreviated “DQ”) and “I” refers to the iodide form of the diquat.

EXAMPLE 2

[0057] Selected diquaternary amines were used to extract PGMs fromsolutions of varying acidity to determine the effect of the PGMsolution's acid strength on the efficacy of the extraction. Eightsolutions Were mixed, each containing a selected diquaternary aminedissolved in a mixture of octanol and chloroform at a concentration of2.5 wt %. Acidic solutions of varying HCL molarity were mixed, eachsolution containing 50 ppm of one of the following metals: Pd II, Pd IV,Pt II, Pt IV, and Rh III. The HCL acid molarities were 0.5 M HCl, 3 MHCl, and 10 M HCl.

[0058] For each of the selected diquaternary amines, the extractionprocedure involved contacting 5 ml of the 2.5% diquatemary aminesolution with 5 ml of one of the acidic mixtures of the PGMs in a 20 mlglass scintillation vial for 30 minutes with vigorous shaking. Phaseseparation was aided by centrifuging the mixture at 2500 rpm for threeminutes. Using a Pasteur pipet, the aqueous phase was then removed,placed in another scintillation vial, and washed by contacting with 10ml of chloroform (1 aqueous:2 organic) for one minute with vigorousshaking. Phase separation was again aided by centrifugation and theaqueous phase was removed, the volume determined, and then analyzed forresidual PGM metal concentration determination. Rh and Pd concentrationswere determined by Atomic Absorption Spectrometry and Pt concentrationsby Inductively Coupled Plasma Atomic Emissions Spectrometry. Theconcentration of metal extracted by the diquaternary amines into theorganic phase was assumed to be the difference between the aqueousphases before and after extraction.

[0059] The results, shown as percent of PGMs extracted, are shown inTables 2-4, supra. As can be seen from Table 2, the selecteddiquaternary amines were significantly better able to extract Pd II andPd IV from the 0.5 M HCl solution than from the higher molaritysolutions. As shown in Table 3, the selected diquaternary amines wereeach highly successful in extracting the Pt II and Pt IV from all thevarying acid molarity solutions. However, as shown in Table 4, only twoof the selected diquaternary amines, 13Cl and 14 Cl, were successful inextracting a significant amount of Rh III from all the various acidmolarity solutions.

[0060] The experiment also analyzed, as shown in each of Tables 2-4, theperformance of ALIQUAT 336 in extracting anions at differing acidity.ALIQUAT 336 is a monoquaternary amine that is used commercially toextract metals from an aqueous solution. In every case, the diquaternaryamines performed significantly better than ALIQUAT 336. Especially inthe case of extracting rhodium, selected diquaternary amines extractedfrom 22% to 30% of the rhodium present in the aqueous acidic solutionswhile ALIQUAT 336 only extracted from 0% to 3%. The results of thisexperiment show that by selecting a particular diquatemary amine as anextractant for a given acidity solution, significantly greater amountsof valuable metals may be extracted from the solutions than usingtraditional extractants.

EXAMPLE 3

[0061] Experiments were conducted using selected diquaternary aminescontacted with acidic solutions of PGMs to determine the relativeselectivity of selected diquaternary amines towards individual PGMs. Anacidic solution containing all three of the PGMs was prepared with thesolution containing 50 ppm each of Rh, Pd, and Pt. Using the extractiontechnique described in Example 2, 2.5% solutions of the selecteddiquatemary amines, dissolved in either chloroform, 1-octanol or amixture of the two, were each contacted with the prepared PGM solution.The results are shown in Table 5, supra. The diquaternary amines wereshown to be most effective when extracting Pt.

[0062] As shown in Table 5, four out of the eight diquaternary aminesshowed promising performance towards both Pt and Pd metals, but the bestperformance was obtained with 13Cl and 14Cl. This fits with the theorythat the performance of the diquaternary amines depends upon the numberof methylenes, and hence the distance, between the two quaternarynitrogens. As shown in Table 5, for diquaternary amines 13Cl and 14Cl,the distance between the quaternary nitrogens is about 3 Å. It should benoted that the average ionic size of the metal halide compounds has beencalculated to be approximately 3 Å, thereby verifying that thediquaternary nitrogen spacing is responsible for causing 13Cl and 14Clto be the best performers.

[0063] Again, as in the last example, ALIQUAT 336 was included as anextractant for analysis and comparison between the performance ofALIQUAT 336, the monoquaternary amine currently used to extract metals,and the diquaternary amines used as described in the present invention.As may be seen in Table 5, selected diquaternary amines extractedsignificantly more rhodium, platinum and palladium than the ALIQUAT 336was able to extract.

EXAMPLE 4

[0064] A catalytic converter from a car made in the United States wasobtained from a junkyard. The converter was opened with a chop saw andtwo monoliths were removed. The back monolith was chopped into piecesand about 203 g of this material was contacted with 375 ml ofconcentrated HCL in a two-liter beaker. About 500 ml of water was addedto cover the material completely and then heated to 50° C. for one hour.The solution was allowed to stand overnight, and then filtered to removethe particulates.

[0065] The solution was analyzed to determine the concentrations of themetal ions present in the solution. The initial concentration of each ofthe metals is shown in FIG. 5. The acid molarity of the solution wasestimated to be 3 M.

[0066] To remove the Pd from the solution, 120 ml of a solution made upof octanol and 0.024 g KI, was contacted with the acid solution for 30minutes. After phase separation, four 10 ml portions were formed fromthe aqueous phase, the remainder being submitted for analysis. Eachportion was separately contacted, by the extraction technique describedin Example 2, with 10 ml of three different extractants: a 5% solutionof the 13Cl diquaternary amine, a solution of ALIQUAT 336 and a solutionof ALAMINE 336. (ALIQUAT 336 and ALAMINE 336 are both registeredtrademarks of the Henkel Corporation of Germany). After phaseseparation, the aqueous phases were removed and submitted for Pt and Pdanalysis. The organic phases were treated with sodium borohydride torecover the extracted metals. The results are shown in FIG. 5.

[0067] As can be seen in FIG. 5, the addition of the KI resulted in theremoval of 98% of the Pd from the solution. In the next step, extractionwith a 5% diquaternary amine in solution with octanol/chloroformselectively removed about 50% of the Pt from the solution. The othercontaminant metals present in the solution, in large excess over thePGMs, were mostly unchanged. By comparison, the commercial productstraditionally used to extract metals from acidic solutions were onlyable to extract a small quantity of the Pd from the solution, while Ptwas not extracted at all.

[0068] It should be noted that the commercial product did not extractany platinum in this example, while in the other examples the commercialproduct did extract platinum. The commercial product is not as selectiveas the diquaternary amines used in the present invention. Therefore,with a large mixture of metals in the metal solution, the commercialproduct selects metals other than the most desirable. By contrast, thediquaternary amines are quite selective and selectively extracted thedesired valuable metals.

[0069] It is apparent that selectively extracting palladium first byusing an iodide is beneficial because it allows the diquaternary aminesto be used for extracting only the other preferred metals. Extractingcapacity by the diquaternary amines is not reduced by having to extractpalladium. Furthermore, it becomes apparent that selected diquaternaryamines may be used in separate extracting processes after the palladiumhas been extracted, each additional extracting process selectivelyextracting one or more valuable metals from the aqueous solution. Forexample, after the palladium has been extracted using an iodide,platinum may be extracted using one diquaternary amine selective forplatinum, and then after separation, rhodium may be extracted using adifferent diquaternary amine selective for rhodium.

[0070] It will be understood from the foregoing description that variousmodifications and changes may be made in the preferred embodiment of thepresent invention without departing from its true spirit. It is intendedthat this description is for purposes of illustration only and shouldnot be construed in a limiting sense. The scope of this invention shouldbe limited only by the language of the following claims.

What is claimed is:
 1. A method for selectively extracting one or moremetal anion complex from an aqueous solution, the method comprising:contacting the aqueous solution with an organic solution including adiquaternary amine, wherein the diquaternary amine has two diquaternarynitrogens spaced at a distance of less than about 10 Å; selectivelybinding the metal anion complex to the diquaternary amine; and thenseparating the organic solution from the aqueous solution, wherein thediquaternary amines having the selectively bound metal anions areconcentrated in the organic solution.
 2. The method of claim 1, whereinthe one or more metal anion complex comprise one or more platinum groupmetals.
 3. The method of claim 1, wherein the one or more metal anioncomplex are selected from anions of Pt, Pd, Rh, and combinationsthereof.
 4. The method of claim 1, wherein the aqueous solutioncomprises anions of one or more metals to be selectively extracted, andanions of contaminant metals.
 5. The method of claim 4, wherein thecontaminant metals are selected from the group consisting of Pb, Al, Ba,Ce, Zr, Fe, Cu, Co, Ni, Mo, Sn, Sb, As, Bi, Zn, Na, K, Ca andcombinations thereof.
 6. The method of claim 1, wherein the one or moremetal anion complex comprise a metal selected from Ag, Au, Pd, Rh, Pt,Ru, Os, Ir, and combinations thereof.
 7. The method of claim 1, whereinthe distance between the two diquaternary nitrogens is between about 5 Åless and 5 Å more than the size of the one or more metal anion complexto be selectively extracted.
 8. The method of claim 1, wherein thedistance between the two diquaternary nitrogens allows the formation ofa complex between both diquaternary nitrogens and the one or more metalanion complex to be selectively extracted.
 9. The method of claim 1,wherein the aqueous solution is acidic.
 10. The method of claim 1,wherein the aqueous solution contains an acid selected from hydrochloricacid, sulfuric acid, nitric acid and combinations thereof.
 11. Themethod of claim 9, wherein the diquaternary amines are characterized inthat the diquaternary amines extract the one or more metal anion complexat all acid concentrations.
 12. The method of claim 1, wherein theaqueous solution is contacted with the organic solution for a timeperiod of less than about 30 minutes.
 13. The method of claim 1, whereinthe aqueous solution is contacted with the organic solution for a timeperiod of less than about 20 minutes.
 14. The method of claim 1, whereinthe aqueous solution is contacted with the organic solution for a timeperiod of between about 5 minutes and about 20 minutes.
 15. The methodof claim 1, wherein the concentration of the diquaternary amines withinthe organic solution is between about 10% and saturation.
 16. The methodof claim 1, wherein the concentration of the diquaternary amines withinthe organic solution is between about 0.5% and about 10%.
 17. The methodof claim 1, wherein the concentration of the diquaternary amines withinthe organic solution are between about 0.5% and about 6%.
 18. The methodof claim 1, wherein the concentration of the diquatemary amines withinthe organic solution are between about 1% and about 5%.
 19. The methodof claim 1, wherein the organic solution has an organic solvent selectedfrom chloroform, 1-octanol, methanol, and combinations thereof.
 20. Themethod of claim 1, wherein the organic solution has any of one or morewater immiscible organic solvents in which the diquaternary amines aresoluble.
 21. The method of claim 1, wherein the diquaternary amine is adiquaternary ammonium halide that is essentially insoluble in water. 22.The method of claim 1, wherein the two diquaternary nitrogens areseparated by an alkyl chain.
 23. The method of claim 22, wherein thealkyl chain is saturated.
 24. The method of claim 22, wherein the alkylchain is unsaturated.
 25. The method of claim 22, wherein the alkylchain is straight.
 26. The method of claim 22, wherein the alkyl chainis branched.
 27. The method of claim 1, wherein the two diquaternarynitrogens are linked in a heterocyclic ring structure.
 28. The method ofclaim 27, wherein the ring structure is saturated.
 29. The method ofclaim 27, wherein the ring structure is unsaturated.
 30. The method ofclaim 27, wherein the ring structure is straight.
 31. The method ofclaim 27, wherein the ring structure is branched.
 32. The method ofclaim 21, wherein the diquaternary ammonium halide comprises a halogenselected from iodine and chlorine.
 33. The method of claim 21, whereinthe diquaternary ammonium halide comprises a halogen selected frombromine and fluorine.
 34. The method of claim 1, wherein the one or moremetal anion complex comprises a metal selected from Pd, Pt, Rh andcombinations thereof, and wherein the two diquaternary nitrogens areseparated by an alkyl chain having 2 to 8 carbon atoms.
 35. The methodof claim 1, wherein the one or more metal anion complex comprises ametal selected from Pd, Pt, Rh and combinations thereof, and wherein thetwo diquaternary nitrogens are separated by an alkyl chain having 2 to 6carbon atoms.
 36. The method of claim 1, wherein the one or more metalanion complex comprises a metal selected from Pd, Pt, Rh andcombinations thereof, and wherein the two diquaternary nitrogens areseparated by an alkyl chain having 2 to 3 carbon atoms.
 37. The methodof claim 34, wherein the diquaternary ammonium halide is a chloride. 38.The method of claim 34, wherein the diquaternary ammonium halide is aniodide.
 39. The method of claim 1, wherein the one or more metal anioncomplex comprises a metal selected from Pd, Pt, Rh and combinationsthereof, and wherein the two diquaternary nitrogens are part of aheterocyclic ring structure having 2 to 8 carbon atoms.
 40. The methodof claim 39, wherein the diquaternary ammonium halide is selected from achloride, an iodide, and combinations thereof.
 41. A method forrecovering Pd and Pt metals from a spent catalyst comprising: dissolvingthe metals into an acidic solution to form metal anion complexes;contacting the acidic solution with an iodide; separating the iodidefrom the acidic solution, wherein the Pd anion complex is bound to theiodide; contacting the acidic solution with an organic solutionincluding a diquaternary amine, wherein the distance between twodiquaternary nitrogens is less than about 10 Å; selectively binding thePt anion complex to the diquaternary amine; and separating the organicsolution from the aqueous solution, wherein the diquaternary amineshaving the bound Pt anion complex are concentrated in the organicsolution.
 42. The method of claim 41, wherein the acidic solutioncontains acids selected from hydrochloric acid, sulfuric acid, nitricacid and combinations thereof.
 43. The method of claim 41, wherein theiodide is selected from potassium iodide, sodium iodide, magnesiumiodide, calcium iodide and combinations thereof.
 44. The method of claim41, wherein the iodide is an organic iodide.
 45. The method of claim 41,wherein the iodide is an inorganic iodide.
 46. A method for recoveringpalladium from an aqueous solution, comprising: contacting the aqueoussolution with an iodide and an organic solvent; allowing the palladiumto bind to the iodide; and then separating the organic solution from theaqueous solution, wherein the iodide having the bound palladium ions areconcentrated in the organic solution.
 47. A method for selectivelyextracting one or more metal anion complex from an aqueous solution, themethod comprising: contacting the aqueous solution with a diquaternaryamine, wherein the distance between two diquaternary nitrogens is lessthan about 10 Å; binding the one or more metal anion complex to thediquaternary amine; and then separating the diquaternary amine from theaqueous solution, wherein the diquaternary amine is bound to a solidsurface of an inert substrate.
 48. The method of claim 47, wherein theone or more metal anion complex comprises one or more platinum groupmetals.
 49. The method of claim 47, wherein the diquaternary amines arebound to a solid surface by means selected from adsorption and chemicalbonding.
 50. The method of claim 47, wherein the inert substrate is apolymer.
 51. A method for recovering valuable metals comprising: a.dissolving the metals into an acidic solution; b. contacting the acidicsolution with an iodide; c. separating the iodide from the acidicsolution, wherein Pd is bound to the iodide; d. contacting the acidicsolution with a first organic solution including a first diquaternaryamine, wherein the distance between two diquaternary nitrogens is lessthan about 10 Å and wherein the first diquaternary amine is a selectiveextractant for a second valuable metal; e. selectively binding thesecond valuable metal anions to the first diquaternary amine; and thenf. separating the organic solution from the aqueous solution, whereinthe first diquaternary amine has the selectively bound second valuablemetal anions concentrated in the organic solution. g. repeating steps dthrough f, using a second diquaternary amine to selectively extract athird valuable metal.